In this paper, α–Fe2O3 photocatalyst with enhanced solar–driven photocatalytic activity was obtained from natural local groundwater sediment using a chemical solution method with subsequent calcination. The phase structures and crystallite size characterized by X–ray diffraction. The morphology and the particle size were investigated by scanning electron microscopy. The α–Fe2O3 was used as a catalyst to photodegrade MB under visible light illumination. The photocatalytic reaction rate constant of the α–Fe2O3 photocatalyst in the photocatalytic degradation of MB dye solution under LED light illumination with the presence of H2O2 was calculated to be 1.70×10–2 min–1. Moreover, the effect of H2O2 concentration on photocatalytic efficiency and the photocatalytic mechanism also were discussed.